焚烧飞灰预处理工艺及其无机氯盐的行为研究

研究表明WCCB(水洗+烧结)预处理工艺能更高效更节能地去除飞灰中的氯化物,以利于其作为水泥原料的使用.水洗工艺条件为两次水洗、水固比均为3∶1,搅拌速度均为150 r.min-1,第一次水洗时间5 min,第二次水洗时间10 min;利用原焚烧炉进行烧结处理,温度为1 000℃,10%氧气含量,停留时间1 h.本研究尝试了3种焚烧飞灰:节煤器出来的飞灰、石灰干法中和酸性气体后布袋收集的飞灰、NaHCO3中和酸性气体后布袋收集的飞灰.经该工艺处理后,焚烧飞灰残渣量减少20%以上,氯减少94%以上,尤以NaHCO3中和得到的飞灰削减量为最,分别达到了72.1%和99.8%.采用同步辐射的X射线吸收近边精细结构(X-ray absorption near edge structure,XANES)和普通X射线衍射(X-ray Diffraction,XRD)相结合的方法研究分析无机氯盐在工艺过程中的行为,发现焚烧飞灰中主要的氯盐主要有NaCl、KCl和CaCl2.焚烧炉烟气净化系统的酸中和剂会影响无机氯盐的生成.焚烧飞灰中难溶性无机氯盐的结构与Friedel’s盐相似,并且与CaCl2有关系.     

应用X射线吸收近边结构谱研究东北农耕土壤中的氯种态及含量

建立了应用X射线吸收近边结构谱(XANES)测定土壤中氯种态及含量的方法并应用该方法对东北地区3种典型农耕土壤(黑土、沼泽土和暗棕壤)进行了分析.本研究以氯化钠、3-氯丙酸以及氯酚红这3种模型化合物谱图作为标准谱图,采用最小二乘法拟合进行定性分析,用一系列不同浓度氯化钠标准谱在2854.80 eV的绝对荧光强度和氯元素浓度线性关系做定量总氯浓度.方法检出限为2 mg·kg-1,相对标准偏差为0%~5%(n=5),回收率为77%~133%.结果表明,研究区土壤总氯含量均值为19 mg·kg-1,其中有机氯平均相对含量高达61%,是无机氯浓度的1~2倍.不同类型土壤中总氯、无机氯和有机氯含量趋势皆为:沼泽土>暗棕壤>黑土.结果表明,XANES法可以无损、全面地测定真实土壤样品中的氯种态及含量,将为进一步研究氯素的地球化学循环提供一定的基础数据.     

Classification of multiple types of organic carbon composition in atmospheric particles by scanning transmission X-ray microscopy analysis

A scanning transmission X-ray microscope at the Lawrence Berkeley National Laboratory is used to measure organic functional group abundance and morphology of atmospheric aerosols. We present a summary of spectra, sizes, and shapes observed in 595 particles that were collected and analyzed between 2000 and 2006. These particles ranged between 0.1 and 12 μm and represent aerosols found in a large range of geographical areas, altitudes, and times. They include samples from seven different field campaigns: PELTI, ACE-ASIA, DYCOMS II, Princeton, MILAGRO (urban), MILAGRO (C-130), and INTEX-B. At least 14 different classes of organic particles show different types of spectroscopic signatures. Different particle types are found within the same region while the same particle types are also found in different geographical domains. Particles chemically resembling black carbon, humic-like aerosols, pine ultisol, and secondary or processed aerosol have been identified from functional group abundance and comparison of spectra with those published in the literature.     

水泥窑共处置含Cr废物中Cr在不同温度下的形态转化

将Na₂CrO₄加入生料中模拟含Cr入窑物料〔掺加比例为0.048%(以w计)〕,以探索水泥窑共处置含Cr废物过程中Cr的形态转化. 将含Cr入窑物料在不同温度条件下进行煅烧,消解煅烧样品以分析Cr在不同温度下的残留率并利用XANES(X射线吸收近边结构光谱)技术分析煅烧样品中Cr的存在形态. 结果表明:对应900、1000、1100、1200、1300和1450℃煅烧条件下,熟料中Cr的残留率分别为88.2%、70.7%、73.7%、67.2%、69.5%和67.8%. 由于窑尾温度为1050～1100℃,并且Cr的残留率在1100℃较高,因此从窑尾添加含Cr废物可以减少水泥窑共处置含Cr废物过程中的Cr逸放. 在900～1450℃煅烧条件下,所有样品中的Cr主要以CrO₃、Cr₂O₃和CaCrO₄的形式存在. 1000℃煅烧温度下存在K₂Cr₂O₇,但不存在K₂CrO₄;900℃和1100～1300℃煅烧温度下有K₂CrO₄存在,但不存在K₂Cr₂O₇. 1100～1450℃煅烧温度下,Cr元素进入到水泥熟料的主要矿物中,并主要以CrO₃和Cr₂O₃的形式与其他物质结合生成了较为复杂的Ca₄A₁₆O₁₂CrO₄、Ca₆Al₄Cr₂O₁₅等.      

六价铬抑制淡水蓝绿藻生长的毒性效应

采用化学品毒性藻类测试的标准方法得到Cr(Ⅵ)抑制蛋白核小球藻、聚球藻、极大螺旋藻、钝顶螺旋藻、羊角月牙藻和四尾栅藻生长的96h-EC₅₀分别为4.96、6.50、11.16、11.74、12.43、20.89mg/L;6种蓝绿藻对Cr(Ⅵ)耐受性大小顺序为:四尾栅藻＞羊角月牙藻＞钝顶螺旋藻＞极大螺旋藻＞聚球藻＞蛋白核小球藻.不同藻类对Cr(Ⅵ)的敏感程度可能与细胞大小和形状、细胞壁结构、藻类分泌物以及酶的作用有关.本文运用X射线吸收近边结构(XANES)初步研究了蛋白核小球藻对Cr(Ⅵ)的吸收和转化.     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

上海地铁站台大气颗粒物中过渡金属研究

采集了上海市地铁站台大气颗粒物PM10和PM2.5样品,研究了颗粒物的形貌、化学元素组成和过渡金属特征.实验发现,地铁站台大气颗粒物PM10和PM2.5质量浓度明显高于室外,超过了国家标准限值.元素组成与室外街道大气颗粒物存在明显差异,过渡金属Fe、Cr、Mn等质量浓度高于室外,Fe是室外含量的8倍,Mn和Cr质量浓度为室外的2倍.扫描电子显微镜(SEM)结果显示地铁内大气颗粒物粒径较大,形状不规则,具有片状刮擦特性.X射线能谱分析(EDX)表明,其主要成分为Fe和O.X射线吸收近边谱(XANES)结果表明,地铁内大气颗粒物PM10中Fe部分以纯Fe(>26%)形态存在,室外街道大气颗粒物PM10中一大部分Fe以Fe(Ⅲ)形态存在.结果显示,对于每天乘坐上海地铁的乘客和在地铁站台内工作的人员,地铁站台是一个重要的存在过渡金属颗粒物暴露的微环境,金属颗粒物对人体健康的影响需要引起重视.     

红壤不同粒级组分中砷的形态——基于连续分级提取和XANES研究

土壤固相由不同大小的土壤颗粒构成.研究砷在土壤不同粒级组分中的形态,有助于深入了解土壤中砷的生物有效性、移动性及其环境风险.本文以砷吸附能力很强的红壤为研究对象,采用传统化学提取法研究了砷在各粒级组分（50～250μm,5～50μm,1～5μm和〈1μm）中的含量和形态,并采用X射线吸收近边结构（XANES）光谱法表征...     

Comprehensive characterization of ambient nanoparticles collected near an industrial science park: Particle size distributions and relationships with environmental factors

We investigated the characteristics of ambient particles and their relationships with various environmental factors, including gaseous pollutants (CH4, non-methane hydrocarbons (NMHC), total hydrocarbons (THC), NOx, CO, SO2), meteorological parameters (humidity, temperature), and time (day/night, workday/weekend). We used an electrical low-pressure cascade impactor to measure the number and size distributions of ambient particles (0.007–10 m) that were collected approximately 1 km northwest of Hsinchu Science Park in Taiwan between February and May 2007. The number concentrations of particles were enhanced through photochemical reactions during the day. In addition, high traffic flow during workdays increased the formation of particulates. Except for SO2, all of the gaseous pollutants we studied (CH4, NMHC, THC, NOx, CO) correlated positively with the total number concentrations of ambient particles during daytime, indicating that they might contribute to the particulate burden. The poorer relationship between the SO2 level and the total number concentration of particles suggests that SO2 might participate indirectly in the nucleation process during particle formation, The high enrichment factors for Zn, Pb, Cu, and Mn, which mostly comprised the ultrafine particles (diameter: < 0.1 m) and fine particles (diameter: 0.1–1 m), presumably arose from emissions from traffic and high technology factories. Heterogeneous reactions on solid particles might play a role in the removal of SOx and NOx from the atmosphere. Sulfides and nitrides can further react with these local pollutants, forming specific Cu-containing compounds: CuO (39%), CuSO4 (34%), and Cu(NO3)2 (27%), within the ambient particles in this industrial area.     

New insights into the sorption mechanism of cadmium on red mud

Effectiveness and mechanism of cadmium (Cd) sorption on original, acidified and ball milling nano-particle red muds were investigated using batch sorption experiments, sequential extraction analysis and X-ray absorption near edge structure (XANES) spectroscopy. The maximum sorption capacity of Cd was 0.16, 0.19, and 0.21 mol/kg for the original, acidified, and nano-particle red muds at pH 6.5, respectively. Both acidification and ball-milling treatments significantly enhanced Cd sorption and facilitated transformation of Cd into less extractable fractions. The Cd L_III-edge XANES analysis indicated the formation of inner-sphere complexes of Cd similar to XCdOH (X represents surface groups on red mud) on the red mud surfaces although outer-sphere complexes of Cd were the primary species. This work shed light on the potential application of red mud to remediate Cd-contaminated soils and illustrated the promising tool of XANES spectroscopy for speciation of multicomponent systems of environmental relevance.